US3950588A - Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes) - Google Patents

Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes) Download PDF

Info

Publication number
US3950588A
US3950588A US05/520,209 US52020974A US3950588A US 3950588 A US3950588 A US 3950588A US 52020974 A US52020974 A US 52020974A US 3950588 A US3950588 A US 3950588A
Authority
US
United States
Prior art keywords
sub
compound
article
formula
perfluorooxyalkylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/520,209
Inventor
Janice E. McDougal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US05/520,209 priority Critical patent/US3950588A/en
Application granted granted Critical
Publication of US3950588A publication Critical patent/US3950588A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/657Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
    • AHUMAN NECESSITIES
    • A47FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47JKITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00Parts, details or accessories of cooking-vessels
    • A47J36/02Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • A47J36/04Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay the materials being non-metallic
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336Polymers modified by chemical after-treatment with organic compounds containing silicon
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544Addition polymer is perhalogenated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164Coating or impregnation specified as water repellent
    • Y10T442/2172Also specified as oil repellent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/273Coating or impregnation provides wear or abrasion resistance

Definitions

  • This invention relates to the treatment of substrates or articles having silanol-reactive surfaces, such as those of glassware, ceramic cookware, and the like, to render said surfaces oil and water repellent and abrasion resistant.
  • the compounds disclosed in the latter patent as useful as oil and water repellents for glass substrates and the like have only a single terminal hydrolyzable silyl group, repeating oxyalkylene units which are exclusively --CF(CF 3 )CF 2 O--, and a terminal perfluoroalkyl group.
  • this invention comprises coating a substrate having at its surface silanol-reactive groups, such as a glass or ceramic substrate, with a coating agent comprising a linear poly(perfluorooxyalkylene) compound terminated on each end with a trisubstituted-silyl group, the poly(perfluorooxyalkylene) portion of such compound comprising at least 80 percent by weight of randomly distributed repeating perfluorooxymethylene and perfluorooxyethylene units, and said substituted silyl groups being readily hydrolyzable to tri-hydroxy silyl groups, thereby providing said surface with a thin, durable, oil and water repellent, abrasion resistant coating or film facilitating the use and extending the life of the substrate, said coating being polysiloxane.
  • a coating agent comprising a linear poly(perfluorooxyalkylene) compound terminated on each end with a trisubstituted-silyl group, the poly(perfluorooxyalkylene) portion of such compound comprising at least 80 percent by
  • a class of di-silyl poly(perfluorooxyalkylene) compounds useful in coating surfaces having silanol-reactive group can be represented by the formula:
  • R fo is a divalent, linear poly(perfluorooxyalkylene) backbone structure having a number average molecular weight, Mn, in the range of 500 to 10,000 or higher, and having the formula:
  • (CF 2 CF 2 O) and (CF 2 O) are randomly distributed oxyethylene and oxymethylene repeating units, respectively, where the subscripts m and n are integers whose ratio m/n is in the range of 0.2/1 to 5/1, preferably 0.5/1 to 2/1
  • X is a hydrolyzable group, such as halo (e.g. chloro, bromo), alkoxy (e.g. methoxy, ethoxy, isopropoxy, butoxy), or acyloxy (e.g. acetoxy), z is an integer of 2 to 11, and Q is a divalent organic linking group which is free of olefinic unsaturation and is stable (e.g.
  • Q are --CON(R')-- (where R' is hydrogen or an alkyl group of 1 to 4 carbon atoms), --CO--, --CO 2 --, --COS--, --NR--, (where R' is hydrogen or an alkyl group of 1 to 4 carbon atoms), arylene having 6 to 15 carbon atoms (e.g. phenylene, --C 6 H 4 --), alkylene, oxaalkylene, and combinations thereof.
  • Q is also free of silanol-reactive groups.
  • a preferred class of said di-silyl poly(perfluorooxyalkylene) compounds are those of the formula:
  • R fo , R', and z are as defined above in the case of formula I, and R" is alkyl having 1 to 4 carbon atoms.
  • di-silyl poly(perfluorooxyalkylene) compounds are generally liquid at ambient temperature and have glass transition temperatures lower than -78°C.
  • the compounds generally will have a number average molecular weight, Mn, in the range of 800 to 20,000 or higher. They are generally moderately soluble and stable in halogenated liquids, e.g. trichlorotrifluoroethane, and inert, completely fluorinated hydrocarbons, e.g. perfluorooctane, and various blends of aprotic polar liquids or hydrocarbons with such halogenated or fluorinated liquids.
  • di-silyl poly(perfluorooxyalkylene) compounds and their preparation, are disclosed in U.S. Pat. No. 3,810,874 (e.g. compound 6 in Table I and Example XXVIII).
  • One method of preparation is by the reaction of an alkyl di-ester of poly(perfluorooxyalkylene) di-acyl fluoride precursor with an aminoalkyltrialkoxysilane such as NH 2 --(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 or NH 2 (CH 2 ) 3 Si(OC 2 H 5 ) 3 .
  • Another method is by the reaction of poly(perfluorooxyalkylene) di-acyl fluoride precursor with aminoalkyltrialkoxysilane.
  • Another method is by reaction of a di-terminally ethylenically unsaturated derivative of poly(perfluorooxyalkylene) di-acyl fluoride precursor, such as the di-alkenylamide, -vinyltriazene, -acrylate, or -vinyl derivatives, with amino-, hydroxy-, or mercapto-substituted silane.
  • Still another method is the reaction of di-amino, -hydroxyl, or -mecapto derivative of the poly(perfluorooxyalkylene) di-acyl fluoride precursor with isocyanato-substituted silane.
  • the above described reactions are disclosed in U.S. Pat. No. 3,646,085 and said U.S. Pat. No. 3,810,874, the latter disclosing said poly(perfluorooxyalkylene) di-acyl fluoride and derivatives and their preparation.
  • the poly(perfluorooxyalkylene) precursors are usually obtained in the form of mixtures of compound having R fo backbones of varying molecular weights and thus the di-silyl derivatives as used in this invention will correspondingly be in the form of mixtures thereof.
  • di-silyl poly(perfluorooxyalkylene) compounds useful in this invention include those of the following formula:
  • the di-silyl poly(perfluorooxyalkylene) treating agents of this invention can be applied to surfaces having silanol-reactive groups, such as hydroxyl, carboxyl and amino, particularly siliceous substrates or articles, such as glass, ceramic, and lithic substrates, cellulosic substrates, such as films and fibers, proteinaceous substrates, such as wool and leather, and the like.
  • silanol-reactive groups such as hydroxyl, carboxyl and amino
  • siliceous substrates or articles such as glass, ceramic, and lithic substrates, cellulosic substrates, such as films and fibers, proteinaceous substrates, such as wool and leather, and the like.
  • Flat glass or window glass such as used for automobile windshields and buildings and the like, glassware, such as used in laboratories or in the home, and ceramic substrates, such as bathroom tiles, sparkplugs, cookware and cooktops, can be treated in accordance with this invention.
  • Treatment of said substrates results in rendering the treated surfaces less retentive of soil and more readily cleaned due to the oil and water repellent nature of the treated surfaces. Also the useful life of the treated substrate, particularly treated glassware, is extended because of the abrasion or scratch resistance of the treated substrate. These desirable properties are maintained despite extended exposure or use and repeated cleanings because of the surprisingly high degree of durability of the treated surface as compared to that heretofore obtainable or known.
  • the coating agent used in this invention can consist of the di-silyl poly(perfluorooxyalkylene) compound per se -- that is, the compound can be used neat -- or, preferably for purposes of efficiency and economics, can be in the form of a dilute solution or dispersion in a volative liquid medium such as aprotic compounds, e.g. ketones such as acetone or methyl ethyl ketone, esters, e.g. ethyl acetate, hydrocarbons, e.g. pentane and toluene, ethers, e.g. diethyl ether, halogenated hydrocarbons, e.g.
  • aprotic compounds e.g. ketones such as acetone or methyl ethyl ketone
  • esters e.g. ethyl acetate
  • hydrocarbons e.g. pentane and toluene
  • ethers e.g. diethyl
  • the concentration of the di-silyl poly(perfluorooxyalkylene) compound in the solution or dispersion can vary, depending upon the particular materials used and the application technique, but generally the concentration will be 0.05 to 50 weight percent or higher.
  • Methods of application of the coating agent to the substrate include brushing, spraying, dipping, rolling, spreading, and the like.
  • the treated substrate can be dried at ambient or elevated temperature, e.g. at 20° to 100°c.
  • One particularly convenient method of application will be that of wiping the substrate with a woven or non-woven, inert fabric or carrier impregnated or containing the coating agent, such carrier being relatively porous and flexible.
  • the impregnated carrier or wipe can be sealed in a moisture-proof package until it is ready to be used.
  • the amount of di-silyl poly)perfluorooxyalkylene) to be coated on the substrate will be that amount sufficient to produce a coating which is water and oil repellent, such a coating having at 20°C a contact angle with distilled water of at least 80°, and a contact angle with n-hexadecane of at least 40°.
  • This coating can be extremely thin, e.g. 1 to 50 molecular layers, though in practice a useful coating may be thicker. Said coating also is durable and abrasion and scratch resistant.
  • the compound Upon contact of the substrate with the di-silyl poly(perfluorooxyalkylene), in the presence of adventitious moisture, the compound becomes firmly bonded to the substrate and forms a cross-linked, relatively transparent polysiloxane film.
  • the substrate to be coated should be relatively dry, that is, though the surface of the substrate to be coated normally will have adsorbed water, the surface should be free of water as a separate phase. And care should also be taken to maintain the coating agent in relatively anhydrous conditions prior to use.
  • the polysiloxane can be considered as being made of repeating units of the formula:
  • the silicon atoms of the repeating units are generally co-valently bonded to oxygen atoms, some of which in turn are bonded to atoms in the substrate surface and others of which are bonded to silicon atoms of adjacent repeating units.
  • poly(perfluorooxyalkylene) is meant to be synonymous to "poly(pefluoroalkylene oxide,” the latter term being employed in the disclosure of said U.S. Pat. No. 3,810,874 which, as mentioned, discloses disilyl poly(perfluorooxyalkylene) compounds, and their preparation, useful as coating agents in this invention.
  • sianol as used herein refers to the ##EQU1## group.
  • the resulting di-silyl poly(perfluorooxyalkylene) product had the structure shown in formula V. Soda lime glass microscope slides coated with this product were found at about 20°C to have an average contact angle with distilled water of 105° and with n-hexadecane of 60°C.
  • a di-silyl poly(perfluorooxyalkylene) product was prepared in the manner similar to that described in Example 1 except that the diester precursor had an Mn of 4000 and the amount of the silane used was 5.5 g. Infrared analysis of the resulting di-silyl poly(perfluorooxyalkylene) product confirmed it as having the structure of said formula V.
  • a di-silyl poly(perfluorooxyalkylene) product was prepared in the manner described in Example 1 except that 10 g of the diester precursor was used and 2.2 g of NH 2 CH 2 CH 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 (sold as "A-1120 Silane") was used as the silane reactant. Infrared analysis confirmed the di-silyl poly(perfluorooxyalkylene) product as having the structure of formula IX.
  • a 1% solution (wt/vol) of the di-silyl poly(perfluorooxyalkylene) product of Example 1 was prepared in a 50/50 solvent blend of 1,1,2-trichloro-1,2,2-trifluoroethane ("Freon 113") and a mixture of saturated fully fluorinated inert fluoroaliphatic compounds boiling at about 100°C. Soda lime glass microscope slides were spread with the 1% solution, the excess solution drained from the slides after 45 seconds, the treated slides dried for 5 min. at about 20°C, and the dried slides rinsed with Freon 113 and buffed with a paper towel. The repellency of the treated surface to various liquids was determined by contact angle measurement, the results being summarized in the following table:
  • the relatively higher contact angle of the treated surface shows a high degree of repellency to liquids.
  • a wipe was prepared by saturating a non-woven web of polyester fibers with a 10% solution (wt/vol) of the di-silyl poly(perfluorooxyalkylene) product of Example 1 in a 50/50 solvent blend of n-pentane and the mixture of fluroaliphatic compounds described in Example 4, and the resulting impregnated web allowed to dry at ambient temperature to remove most of the solvent. Soda lime glass microscope slides were then rubbed with the wipe, the treated surfaces allowed to dry for about 30 min. at ambient temperature, and the dried surfaces buffed with a paper towel. The contact angles of distilled water on the treated surfaces averaged 96°, demonstrating again the high degree of water repellency of the treated surface.
  • Example 6 Vertical glass plates were spray coated and dried in the same manner described in Example 6. The resulting treated surfaces were found to have an average contact angle of 108° with distilled water. After 200 cycles of abrasion of the treated surfaces with a "Tabor Abrader," having a rubber wheel covered with cheesecloth and under a 1000 g load, the treated surfaces were found to have essentially the same contact angle with distilled water, demonstrating the abrasion resistance of the treated surfaces.
  • Soda lime microscope glass slides were treated with coating agent in the manner described in Example 4 and the treated slides tested to determine the durability of the treated surface after repeated washing in hot detergent solution. Each washing cycle consisted of
  • Results are set forth in the following table together with, for purposes of comparison, the results obtained by treating glass slides with "Rain.X" and "Total Finish," commercial automotive polysiloxane glass treating agents.
  • the Rain.X was applied to the glass slides with cheesecloth dampened with the Rain.X coating agent and the slides then dried for 1 min. and buffed with paper towel, according to the directions supplied by the manufacturer.
  • the Total Finish was applied in the same manner except that drying was accomplished over night, according to the manufacturer's directions.
  • Soda lime microscope glass slides were coated as in Example 4. Following the evaporation of the solvent, the slides were rinsed in Freon 113 and allowed to air dry without buffing. The thus prepared slides were then subjected to the same detergent wash durability test described in Example 8 except that, following the treatment with acetone, the slides were not buffed. As in Example 8, the contact angle of distilled water was determined periodically.
  • other glass slides were treated with three commercial products (viz. "Dri-Film” SC-87, "Siliclad,” and “Glasskote”) sold for the treatment of laboratory glassware. In using these commercial products, solutions were made following the manufacturer's directions.
  • the "Dri-Film” SC-87 was coated from a 10% solution of Dri-Film in decane and the slides then dried for 30 min. at 100°C.
  • the "Siliclad” was made into a 1% solution in warm water, the slides dipped in the solution for 10 seconds, the treated slides rinsed under running water and then oven-dried for 10 min. at 100°C.
  • the "Glasskote” was sprayed on the slides and the treated slides then rinsed under running water and oven-dried for 10 min. at 100°C.
  • Soda lime glass microscope slides were coated in a manner similar to Example 4 with a 1% (wt/vol) Freon 113 solution of the di-silyl poly(perfluorooxyalkylene) product of Example 1.
  • Contact angles of distilled water on the treated surfaces averaged 100°. Chemical resistance was then tested in two different manners: in one manner, the given chemical was wiped on the treated surface, the surface rinsed under running water, wiped dry, the chemical reapplied, again rinsed and dried, and this procedure repeated for 25 cycles; in the other manner, the treated slides were soaked in the chemical for 164 hours and then rinsed under running water and dried.
  • Wipes prepared as described in Example 5 were used to treat a number of "Pyrex" glass beakers. When only the lips of the beakers were treated with the wipe, and water was poured from the beakers and the beakers set upright, no drips ran down the outside of the beakers from the treated lips. Additionally, when the whole interior surface of the beakers was treated with the wipe, and water was poured out of the beakers, no clinging of liquid was observed on the interior wall or bottom of the beakers. In contrast, untreated beakers were found to have drips running down the outsides of the beakers and significant water clinging to the insides of the beakers. Similar differences were noted with a variety of other liquids.
  • a glass buret was treated with a 1% Freon 113 solution of the di-silyl poly(perfluorooxyalkylene) product of Example 1 by filling the buret with the solution, draining the buret after 1 min., and rinsing the buret with Freon 113.
  • the resulting treated buret no longer exhibited a meniscus when filled with water and the treated buret could be read accurately immediately after a portion of the liquid was removed therefrom without the necessity of waiting for the liquid to drain.
  • Example 8 A 1% Freon 113 solution of di-silyl poly(perfluorooxyalkylene) product of Example 1 was used in the treatment of glazed ceramic bathroom tiles. From the manner in which water beaded up on the treated surfaces of the tiles, the contact angle was estimated to be greater than 90°, demonstrating the repellent nature of the treated surface. This degree of repellency was retained through 50 hot detergent cycles run as described in Example 8.
  • One-half of a commercial ceramic cooking surface was treated with the wipe described in Example 5. Food was deliberately burned on the cooking surface and it was found that the treated portion of the cooking surface was much easier to clean than the untreated portion of the surface, the treated portion requiring less than one-half of the number of applications of a commercial cleanser to remove the burned-on stains.
  • One-half of the outside of the clean windshield of an automobile was spray coated with the 1% solution of di-silyl poly(perfluorooxyalkylene) product of Example 4, the coated windshield allowed to dry at ambient temperature for about 10 min. and then buffed to transparency with paper towels wet with Freon 113. Over a period of six months of normal use of the automobile, notably superior visibility in rain through the treated portion of the windshield was experienced. The treated portion of the windshield also stayed cleaner and released frost easier, as compared to the untreated portion.
  • Example 4 The outside of a number of cleaned windows of a house were spray coated with the 1% coating solution described in Example 4.
  • the coated windows were allowed to dry in air at ambient temperature for several minutes and then buffed to transparency with paper towel.
  • the coated windows were examined over the course of several weeks and were found to be considerably cleaner than untreated windows of the house.
  • One lens of each of a number of pairs of eyeglasses was treated with a wipe of the type described in Example 5.
  • the treated lens of each pair was easier to maintain in a clean condition than the untreated lens even after two months of use.

Abstract

Substrates or articles having surfaces with silanol-reactive groups, e.g. glassware and ceramic cookware having hydroxylic surfaces, are coated with hydrolyzable di-silyl poly(perfluorooxyalkylene) compounds to provide said substrates or articles with a durable, oil and water repellent, abrasion resistant polysiloxane coating or film.

Description

This invention relates to the treatment of substrates or articles having silanol-reactive surfaces, such as those of glassware, ceramic cookware, and the like, to render said surfaces oil and water repellent and abrasion resistant.
Though various perfluoroalkyl-containing silanes and siloxanes have been proposed or used heretofore in the treatment of glass and ceramic articles and the like to render the same oil and water repellent and abrasion resistant (e.g. see U.S. Pat. Nos. 3,423,234, 3,442,664, 3,666,538, and 3,772,346), prior art which appears to be most pertinent to the invention in the instant application is U.S. Pat. No. 3,646,085. However, the compounds disclosed in the latter patent as useful as oil and water repellents for glass substrates and the like have only a single terminal hydrolyzable silyl group, repeating oxyalkylene units which are exclusively --CF(CF3)CF2 O--, and a terminal perfluoroalkyl group.
Briefly, this invention comprises coating a substrate having at its surface silanol-reactive groups, such as a glass or ceramic substrate, with a coating agent comprising a linear poly(perfluorooxyalkylene) compound terminated on each end with a trisubstituted-silyl group, the poly(perfluorooxyalkylene) portion of such compound comprising at least 80 percent by weight of randomly distributed repeating perfluorooxymethylene and perfluorooxyethylene units, and said substituted silyl groups being readily hydrolyzable to tri-hydroxy silyl groups, thereby providing said surface with a thin, durable, oil and water repellent, abrasion resistant coating or film facilitating the use and extending the life of the substrate, said coating being polysiloxane.
A class of di-silyl poly(perfluorooxyalkylene) compounds useful in coating surfaces having silanol-reactive group can be represented by the formula:
R.sub.fo {--Q(CH.sub.2).sub.z Si(X).sub. 3 }.sub.2         I
where Rfo is a divalent, linear poly(perfluorooxyalkylene) backbone structure having a number average molecular weight, Mn, in the range of 500 to 10,000 or higher, and having the formula:
--CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.m (CF.sub.2 O).sub.n --CH.sub.2 --II
where (CF2 CF2 O) and (CF2 O) are randomly distributed oxyethylene and oxymethylene repeating units, respectively, where the subscripts m and n are integers whose ratio m/n is in the range of 0.2/1 to 5/1, preferably 0.5/1 to 2/1, X is a hydrolyzable group, such as halo (e.g. chloro, bromo), alkoxy (e.g. methoxy, ethoxy, isopropoxy, butoxy), or acyloxy (e.g. acetoxy), z is an integer of 2 to 11, and Q is a divalent organic linking group which is free of olefinic unsaturation and is stable (e.g. resistant to hydrolysis) under the conditions of said surface treatment. Representative examples of Q are --CON(R')-- (where R' is hydrogen or an alkyl group of 1 to 4 carbon atoms), --CO--, --CO2 --, --COS--, --NR--, (where R' is hydrogen or an alkyl group of 1 to 4 carbon atoms), arylene having 6 to 15 carbon atoms (e.g. phenylene, --C6 H4 --), alkylene, oxaalkylene, and combinations thereof. Q is also free of silanol-reactive groups.
A preferred class of said di-silyl poly(perfluorooxyalkylene) compounds are those of the formula:
R.sub.fo {--CON(R')(CH.sub.2).sub.z Si(OR").sub.3 }.sub.2  III
where Rfo, R', and z are as defined above in the case of formula I, and R" is alkyl having 1 to 4 carbon atoms.
The above-described di-silyl poly(perfluorooxyalkylene) compounds are generally liquid at ambient temperature and have glass transition temperatures lower than -78°C. The compounds generally will have a number average molecular weight, Mn, in the range of 800 to 20,000 or higher. They are generally moderately soluble and stable in halogenated liquids, e.g. trichlorotrifluoroethane, and inert, completely fluorinated hydrocarbons, e.g. perfluorooctane, and various blends of aprotic polar liquids or hydrocarbons with such halogenated or fluorinated liquids.
Some of said di-silyl poly(perfluorooxyalkylene) compounds, and their preparation, are disclosed in U.S. Pat. No. 3,810,874 (e.g. compound 6 in Table I and Example XXVIII). One method of preparation is by the reaction of an alkyl di-ester of poly(perfluorooxyalkylene) di-acyl fluoride precursor with an aminoalkyltrialkoxysilane such as NH2 --(CH2)2 NH(CH2)3 Si(OCH3)3 or NH2 (CH2)3 Si(OC2 H5)3. Another method is by the reaction of poly(perfluorooxyalkylene) di-acyl fluoride precursor with aminoalkyltrialkoxysilane. Another method is by reaction of a di-terminally ethylenically unsaturated derivative of poly(perfluorooxyalkylene) di-acyl fluoride precursor, such as the di-alkenylamide, -vinyltriazene, -acrylate, or -vinyl derivatives, with amino-, hydroxy-, or mercapto-substituted silane. Still another method is the reaction of di-amino, -hydroxyl, or -mecapto derivative of the poly(perfluorooxyalkylene) di-acyl fluoride precursor with isocyanato-substituted silane. The above described reactions are disclosed in U.S. Pat. No. 3,646,085 and said U.S. Pat. No. 3,810,874, the latter disclosing said poly(perfluorooxyalkylene) di-acyl fluoride and derivatives and their preparation. The poly(perfluorooxyalkylene) precursors are usually obtained in the form of mixtures of compound having Rfo backbones of varying molecular weights and thus the di-silyl derivatives as used in this invention will correspondingly be in the form of mixtures thereof.
Representatives di-silyl poly(perfluorooxyalkylene) compounds useful in this invention include those of the following formula:
R.sub.fo {--CONH(CH.sub.2).sub.3 Si(OCH.sub.3).sub.3 }.sub.2 IV
r.sub.fo {--CONH(CH.sub.2).sub.3 Si(OC.sub.2 H.sub.5).sub.3 }.sub.2 V
r.sub.fo {--CH.sub.2 NHCOS(CH.sub.2).sub.3 Si(OCH(CH.sub.3).sub.2).sub.3 }.sub.2                                                   VI
r.sub.fo {--CH.sub.2 S(CH.sub.2).sub.3 SiCl.sub.3 }.sub.2  VII
r.sub.fo {--CONH(CH.sub.2).sub.3 Si(O.sub.2 CCH.sub.3).sub.3 }.sub.2 VIII
r.sub.fo {--CONH(CH.sub.2).sub.2 NH(CH.sub.2).sub.3 Si(OCH.sub.3).sub.3 }.sub.2                                                   IX
the di-silyl poly(perfluorooxyalkylene) treating agents of this invention can be applied to surfaces having silanol-reactive groups, such as hydroxyl, carboxyl and amino, particularly siliceous substrates or articles, such as glass, ceramic, and lithic substrates, cellulosic substrates, such as films and fibers, proteinaceous substrates, such as wool and leather, and the like. Flat glass or window glass, such as used for automobile windshields and buildings and the like, glassware, such as used in laboratories or in the home, and ceramic substrates, such as bathroom tiles, sparkplugs, cookware and cooktops, can be treated in accordance with this invention.
Treatment of said substrates results in rendering the treated surfaces less retentive of soil and more readily cleaned due to the oil and water repellent nature of the treated surfaces. Also the useful life of the treated substrate, particularly treated glassware, is extended because of the abrasion or scratch resistance of the treated substrate. These desirable properties are maintained despite extended exposure or use and repeated cleanings because of the surprisingly high degree of durability of the treated surface as compared to that heretofore obtainable or known.
The coating agent used in this invention can consist of the di-silyl poly(perfluorooxyalkylene) compound per se -- that is, the compound can be used neat -- or, preferably for purposes of efficiency and economics, can be in the form of a dilute solution or dispersion in a volative liquid medium such as aprotic compounds, e.g. ketones such as acetone or methyl ethyl ketone, esters, e.g. ethyl acetate, hydrocarbons, e.g. pentane and toluene, ethers, e.g. diethyl ether, halogenated hydrocarbons, e.g. trichlorotrifluoroethane, completely fluorinated hydrocarbons, e.g. perfluorooctane, and various blends of these materials. The concentration of the di-silyl poly(perfluorooxyalkylene) compound in the solution or dispersion can vary, depending upon the particular materials used and the application technique, but generally the concentration will be 0.05 to 50 weight percent or higher.
Methods of application of the coating agent to the substrate include brushing, spraying, dipping, rolling, spreading, and the like. Following application, the treated substrate can be dried at ambient or elevated temperature, e.g. at 20° to 100°c. One particularly convenient method of application will be that of wiping the substrate with a woven or non-woven, inert fabric or carrier impregnated or containing the coating agent, such carrier being relatively porous and flexible. The impregnated carrier or wipe can be sealed in a moisture-proof package until it is ready to be used.
The amount of di-silyl poly)perfluorooxyalkylene) to be coated on the substrate will be that amount sufficient to produce a coating which is water and oil repellent, such a coating having at 20°C a contact angle with distilled water of at least 80°, and a contact angle with n-hexadecane of at least 40°. This coating can be extremely thin, e.g. 1 to 50 molecular layers, though in practice a useful coating may be thicker. Said coating also is durable and abrasion and scratch resistant.
Upon contact of the substrate with the di-silyl poly(perfluorooxyalkylene), in the presence of adventitious moisture, the compound becomes firmly bonded to the substrate and forms a cross-linked, relatively transparent polysiloxane film. In order to promote such reaction, the substrate to be coated should be relatively dry, that is, though the surface of the substrate to be coated normally will have adsorbed water, the surface should be free of water as a separate phase. And care should also be taken to maintain the coating agent in relatively anhydrous conditions prior to use.
The polysiloxane can be considered as being made of repeating units of the formula:
--O.sub.3/2 Si(CH.sub.2).sub.z QR.sub.fo Q(CH.sub.2).sub.z SiO.sub.3/2 -- X
where Q, Rfo, and z are as defined in formula I. In the polysiloxane structure, the silicon atoms of the repeating units are generally co-valently bonded to oxygen atoms, some of which in turn are bonded to atoms in the substrate surface and others of which are bonded to silicon atoms of adjacent repeating units.
In this application, the term "poly(perfluorooxyalkylene)" is meant to be synonymous to "poly(pefluoroalkylene oxide," the latter term being employed in the disclosure of said U.S. Pat. No. 3,810,874 which, as mentioned, discloses disilyl poly(perfluorooxyalkylene) compounds, and their preparation, useful as coating agents in this invention. The term "silanol" as used herein refers to the ##EQU1## group.
The formation of the latter group from the terminal hydrolyzable silyl groups of the poly(perfluorooxyalkylene) compound will require, as is known in the art, hydrolyzing conditions, viz. the presence of at least a stoichiometric amount of water, which amount is readily available from adventitious moisture in the ambient atmosphere at a relative humidity, for example, of 25% or higher.
Objects and advantages of this invention are illustrated in the following examples but the various materials and amounts recited therein, as well as conditions and other details, should not be construed to unduly limit this invention.
EXAMPLE 1
In a 100 ml glass flask, equipped with a magnetic stirrer and dropping funnel and maintained under a nitrogen atmosphere, was charged 50 g of the diester CH3 O2 C--CF2 O(CF2 CF2 O)m (CF2 O)n CF2 --CO2 CH3 (Mn = 2000, m/n = 0.7). Over a period of 15 min., 11.0 g of the silane H2 N(CH2)3 Si(OC2 H5)3 (sold as "A-1100 Silane") was added and the resulting solution stirred at room temperature for 16 hrs. The resulting reacted solution was then subjected to reduced pressure (1 Torr) at 50°C to remove the methanol liberated during the reaction. As confirmed by infrared analysis, the resulting di-silyl poly(perfluorooxyalkylene) product had the structure shown in formula V. Soda lime glass microscope slides coated with this product were found at about 20°C to have an average contact angle with distilled water of 105° and with n-hexadecane of 60°C.
EXAMPLE 2
A di-silyl poly(perfluorooxyalkylene) product was prepared in the manner similar to that described in Example 1 except that the diester precursor had an Mn of 4000 and the amount of the silane used was 5.5 g. Infrared analysis of the resulting di-silyl poly(perfluorooxyalkylene) product confirmed it as having the structure of said formula V.
EXAMPLE 3
A di-silyl poly(perfluorooxyalkylene) product was prepared in the manner described in Example 1 except that 10 g of the diester precursor was used and 2.2 g of NH2 CH2 CH2 NH(CH2)3 Si(OCH3)3 (sold as "A-1120 Silane") was used as the silane reactant. Infrared analysis confirmed the di-silyl poly(perfluorooxyalkylene) product as having the structure of formula IX.
EXAMPLE 4
A 1% solution (wt/vol) of the di-silyl poly(perfluorooxyalkylene) product of Example 1 was prepared in a 50/50 solvent blend of 1,1,2-trichloro-1,2,2-trifluoroethane ("Freon 113") and a mixture of saturated fully fluorinated inert fluoroaliphatic compounds boiling at about 100°C. Soda lime glass microscope slides were spread with the 1% solution, the excess solution drained from the slides after 45 seconds, the treated slides dried for 5 min. at about 20°C, and the dried slides rinsed with Freon 113 and buffed with a paper towel. The repellency of the treated surface to various liquids was determined by contact angle measurement, the results being summarized in the following table:
                      Contact angle                                       
                                 Contact angle                            
                      on untreated                                        
                                 on treated                               
Test     Test liquid  surface    surface                                  
______________________________________                                    
1    Distilled H.sub.2 O                                                  
                      11° 98°                               
2    2-Ethyl-1-hexanol                                                    
                      (too low to                                         
                                 29°                               
                        measure)                                          
3    Motor Oil ("Penzoil"                                                 
                      15° 57°                               
          10W-20W-30)                                                     
4    Glycerol         23° 93°                               
5    Aqueous NaCl (50% sat'd)                                             
                      13° 103°                              
6    Aqueous CaCl.sub.2 (50% sat'd)                                       
                      20° 103°                              
7    Corn syrup ("Karo")                                                  
                      47° 105°                              
8    Vegetable oil ("Crisco")                                             
                      15° 62°                               
______________________________________                                    
The relatively higher contact angle of the treated surface shows a high degree of repellency to liquids.
EXAMPLE 5
A wipe was prepared by saturating a non-woven web of polyester fibers with a 10% solution (wt/vol) of the di-silyl poly(perfluorooxyalkylene) product of Example 1 in a 50/50 solvent blend of n-pentane and the mixture of fluroaliphatic compounds described in Example 4, and the resulting impregnated web allowed to dry at ambient temperature to remove most of the solvent. Soda lime glass microscope slides were then rubbed with the wipe, the treated surfaces allowed to dry for about 30 min. at ambient temperature, and the dried surfaces buffed with a paper towel. The contact angles of distilled water on the treated surfaces averaged 96°, demonstrating again the high degree of water repellency of the treated surface.
EXAMPLE 6
Vertical glass plates were spray coated with a 0.25% (wt/vol) solution of the di-silyl poly(perfluorooxyalkylene) product of Example 1 in Freon 113 and the treated surfaces buffed with paper towel. The treated surfaces were found to have an average contact angle of 106° with distilled water whereas untreated glass plates had a contact angle of only 35° with distilled water, again demonstrating the high degree of water repellency of the treated surface. After 300 hours under "Weather-O-Meter" test conditions (equivalent to 12 months exposure to actual atmospheric conditions), the average contact angles of the treated surfaces were 94° with distilled water, demonstrating the durability of the treated surfaces.
EXAMPLE 7
Vertical glass plates were spray coated and dried in the same manner described in Example 6. The resulting treated surfaces were found to have an average contact angle of 108° with distilled water. After 200 cycles of abrasion of the treated surfaces with a "Tabor Abrader," having a rubber wheel covered with cheesecloth and under a 1000 g load, the treated surfaces were found to have essentially the same contact angle with distilled water, demonstrating the abrasion resistance of the treated surfaces. When the other similarly treated glass plates were subjected to the abrasive action of a "Tabor Abrader" using an abrasive wheel (CS-10F) under a 1000 g load, it was found that only after 700 cycles did the treated surface have a contact angle with distilled water that was essentially the same as that of the untreated surface, by which time the treated glass surface was found to be scratched.
EXAMPLE 8
Soda lime microscope glass slides were treated with coating agent in the manner described in Example 4 and the treated slides tested to determine the durability of the treated surface after repeated washing in hot detergent solution. Each washing cycle consisted of
1. Immersing the treated glass slides for 1 min. at 80°C in a 1% detergent solution of "Alconox";
2. Rinsing with running water;
3. Drying with acetone; and
4. Buffing the treated surface with paper towel. The contact angle of distilled water on the treated surfaces was periodically determined. Results are set forth in the following table together with, for purposes of comparison, the results obtained by treating glass slides with "Rain.X" and "Total Finish," commercial automotive polysiloxane glass treating agents. The Rain.X was applied to the glass slides with cheesecloth dampened with the Rain.X coating agent and the slides then dried for 1 min. and buffed with paper towel, according to the directions supplied by the manufacturer. The Total Finish was applied in the same manner except that drying was accomplished over night, according to the manufacturer's directions.
______________________________________                                    
       Contact angle with distilled water                                 
         1% soln. of                                                      
Cycles   di-silyl compound                                                
                       Rain.sup.. X                                       
                                 Total Finish                             
______________________________________                                    
 0       106°   92°                                         
                                 96°                               
 5       106°   68°                                         
                                 93°                               
10       108°   45°                                         
                                 89°                               
15       105°   --        71°                               
25       104°   --        --                                       
50       100°   --        --                                       
______________________________________                                    
The data of the above table demonstrate the superior durability of the di-silyl compound coating in that the contact angle remained substantially constant for at least the first 25 cycles.
EXAMPLE 9
Soda lime microscope glass slides were coated as in Example 4. Following the evaporation of the solvent, the slides were rinsed in Freon 113 and allowed to air dry without buffing. The thus prepared slides were then subjected to the same detergent wash durability test described in Example 8 except that, following the treatment with acetone, the slides were not buffed. As in Example 8, the contact angle of distilled water was determined periodically. For purposes of comparison, other glass slides were treated with three commercial products (viz. "Dri-Film" SC-87, "Siliclad," and "Glasskote") sold for the treatment of laboratory glassware. In using these commercial products, solutions were made following the manufacturer's directions. The "Dri-Film" SC-87 was coated from a 10% solution of Dri-Film in decane and the slides then dried for 30 min. at 100°C. The "Siliclad" was made into a 1% solution in warm water, the slides dipped in the solution for 10 seconds, the treated slides rinsed under running water and then oven-dried for 10 min. at 100°C. The "Glasskote" was sprayed on the slides and the treated slides then rinsed under running water and oven-dried for 10 min. at 100°C. These three sets of comparison slides were then subjected to the same detergent wash durability test and the contact angles of distilled water were likewise determined periodically. Results of these tests are set forth in the following table:
Contact angle with distilled water                                        
       1% soln. of   Dri-Film                                             
Cycles di-silyl compound                                                  
                     SC-87     Glasskote                                  
                                       Siliclad                           
______________________________________                                    
 0     112°   87°                                           
                               57°                                 
                                       75°                         
 5     107°   90°                                           
                               22°                                 
                                       53°                         
10     105°   85°                                           
                               --      45°                         
15     101°   80°                                           
                               --      --                                 
20     103°   73°                                           
                               --      --                                 
25     100°   --        --      --                                 
50     100°   --        --      --                                 
______________________________________                                    
These data show that the water repellency of the di-silyl compound coating was initially, and even after 50 cycles, greater than that of the other coatings initially.
EXAMPLE 10
Soda lime glass microscope slides were coated in a manner similar to Example 4 with a 1% (wt/vol) Freon 113 solution of the di-silyl poly(perfluorooxyalkylene) product of Example 1. Contact angles of distilled water on the treated surfaces averaged 100°. Chemical resistance was then tested in two different manners: in one manner, the given chemical was wiped on the treated surface, the surface rinsed under running water, wiped dry, the chemical reapplied, again rinsed and dried, and this procedure repeated for 25 cycles; in the other manner, the treated slides were soaked in the chemical for 164 hours and then rinsed under running water and dried. Of 40 representative chemicals tested (acids, anhydrides, aliphatic and aromatic hydrocarbons, alcohols, amines, esters, ethers, ketones, chlorinated and polymer solvents, inorganic bases, peroxides, halogens, salt solutions), only hydrofluoric acid (49%), aqua regia, aqueous sodium hydroxide (50%), and aqueous ferric chloride (25%) caused significant reduction in contact angle of distilled water.
EXAMPLE 11
Wipes prepared as described in Example 5 were used to treat a number of "Pyrex" glass beakers. When only the lips of the beakers were treated with the wipe, and water was poured from the beakers and the beakers set upright, no drips ran down the outside of the beakers from the treated lips. Additionally, when the whole interior surface of the beakers was treated with the wipe, and water was poured out of the beakers, no clinging of liquid was observed on the interior wall or bottom of the beakers. In contrast, untreated beakers were found to have drips running down the outsides of the beakers and significant water clinging to the insides of the beakers. Similar differences were noted with a variety of other liquids.
A glass buret was treated with a 1% Freon 113 solution of the di-silyl poly(perfluorooxyalkylene) product of Example 1 by filling the buret with the solution, draining the buret after 1 min., and rinsing the buret with Freon 113. The resulting treated buret no longer exhibited a meniscus when filled with water and the treated buret could be read accurately immediately after a portion of the liquid was removed therefrom without the necessity of waiting for the liquid to drain.
EXAMPLE 12
A 1% Freon 113 solution of di-silyl poly(perfluorooxyalkylene) product of Example 1 was used in the treatment of glazed ceramic bathroom tiles. From the manner in which water beaded up on the treated surfaces of the tiles, the contact angle was estimated to be greater than 90°, demonstrating the repellent nature of the treated surface. This degree of repellency was retained through 50 hot detergent cycles run as described in Example 8.
EXAMPLE 13
"Pyrex" glass cake pans and a "Corningware" ceramic casserole dish were wiped with a 1% Freon 113 solution of the di-silyl poly(perfluorooxyalkylene) product of Example 1. The treated bakeware was used repeatedly to bake cakes and casseroles and after each use was found to readily release baked food residue when washed, as compared to the results obtained when untreated bakeware was used.
One-half of a commercial ceramic cooking surface was treated with the wipe described in Example 5. Food was deliberately burned on the cooking surface and it was found that the treated portion of the cooking surface was much easier to clean than the untreated portion of the surface, the treated portion requiring less than one-half of the number of applications of a commercial cleanser to remove the burned-on stains.
The lip of a "Pyroceram" cream pitcher was treated with the above-described wipe and when the contents of the pitcher were poured and the pitcher placed upright, no drips formed along the exterior of the pitcher.
EXAMPLE 14
One-half of the outside of the clean windshield of an automobile was spray coated with the 1% solution of di-silyl poly(perfluorooxyalkylene) product of Example 4, the coated windshield allowed to dry at ambient temperature for about 10 min. and then buffed to transparency with paper towels wet with Freon 113. Over a period of six months of normal use of the automobile, notably superior visibility in rain through the treated portion of the windshield was experienced. The treated portion of the windshield also stayed cleaner and released frost easier, as compared to the untreated portion.
EXAMPLE 15
The outside of a number of cleaned windows of a house were spray coated with the 1% coating solution described in Example 4. The coated windows were allowed to dry in air at ambient temperature for several minutes and then buffed to transparency with paper towel. The coated windows were examined over the course of several weeks and were found to be considerably cleaner than untreated windows of the house.
EXAMPLE 16
One lens of each of a number of pairs of eyeglasses was treated with a wipe of the type described in Example 5. The treated lens of each pair was easier to maintain in a clean condition than the untreated lens even after two months of use.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.

Claims (10)

What is claimed is:
1. A porous, woven or non-woven, inert, resilient carrier impregnated with a linear poly(perfluorooxyalkylene) compound terminated on each end with a trisubstituted-silyl group hydrolyzable to a tri-hydroxysilyl group, said compound having the formula:
R.sub.fo {--Q(CH.sub.2).sub.z Si(X).sub.3 }.sub.2
where Rfo is a divalent, linear poly(perfluorooxyalkylene) backbone structure having a number average molecular weight in the range of 500 to 10,000 and has the formula:
--CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.m (CF.sub.2 O).sub.n --CF.sub.2 --
where (CF2 CF2 O) and (CF2 O) are randomly distributed oxyethylene and oxymethylene repeating units, respectively, where the subscripts m and n are integers whose ratio m/n is in the range of 0.2/1 to 5/1, X is a hydrolyzable group selected from the group consisting of halo, alkoxy, and acyloxy, z is an integer of 2 to 11, and Q is a divalent organic linking group which is free of olefinic unsaturation and silanol-reactive groups.
2. The article of claim 1, wherein said compound has at least 40 wt % carbon-bonded fluorine in the form of perfluorooxyalkylene.
3. The article of claim 1, wherein Q is --CON(R')--, where R' is hydrogen or an alkyl group of 1 to 4 carbon atoms, and X is an alkoxy group having 1 to 4 carbon atoms.
4. The article of claim 1, wherein said carrier comprises a non-woven web of polyester fibers.
5. The article of claim 1, wherein said compound has the formula
R.sub.fo {--CONH(CH.sub.2).sub.3 Si(OCH.sub.3).sub.3 }.sub.2
where Rfo is as defined in claim 1.
6. The article of claim 1, wherein said compound has the formula
R.sub.fo {--CONH(CH.sub.2).sub.3 Si(OC.sub.2 H.sub.5).sub.3 }.sub.2
where Rfo is as defined in claim 1.
7. The article of claim 1, wherein said compound has the formula
R.sub.fo {--CH.sub.2 NHCOS(CH.sub.2).sub.3 Si(OCH(CH.sub.3).sub.2).sub.3 }.sub.2
where Rfo is as defined in claim 1.
8. The article of claim 1, wherein said compound has the formula
R.sub.fo {--CH.sub.2 S(CH.sub.2).sub.3 SiCl.sub.3 }.sub.2
where Rfo is as defined in claim 1.
9. The article of claim 1, wherein said compound has the formula
R.sub.fo {--CONH(CH.sub.2).sub.3 Si(O.sub.2 CCH.sub.3).sub.3 }.sub.2
where Rfo is as defined in claim 1.
10. The article of claim 1, wherein said compound has the formula
R.sub.fo {--CONH(CH.sub.2).sub.2 NH(CH.sub.2).sub.3 Si(OCH.sub.3).sub.3 }.sub.2
where Rfo is as defined in claim 1.
US05/520,209 1974-11-01 1974-11-01 Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes) Expired - Lifetime US3950588A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/520,209 US3950588A (en) 1974-11-01 1974-11-01 Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/520,209 US3950588A (en) 1974-11-01 1974-11-01 Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes)

Publications (1)

Publication Number Publication Date
US3950588A true US3950588A (en) 1976-04-13

Family

ID=24071624

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/520,209 Expired - Lifetime US3950588A (en) 1974-11-01 1974-11-01 Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes)

Country Status (1)

Country Link
US (1) US3950588A (en)

Cited By (76)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302571A (en) * 1979-03-16 1981-11-24 Shin-Etsu Chemical Co., Ltd. Room temperature-curable polyoxyalkylene polyether compositions
US4316041A (en) * 1980-02-19 1982-02-16 Union Carbide Corporation Liquid crystal silanes
US4322542A (en) * 1980-01-17 1982-03-30 Varian Associates, Inc. Strong anion exchange composition
US4342796A (en) * 1980-09-10 1982-08-03 Advanced Chemical Technologies, Inc. Method for inhibiting corrosion of internal structural members of reinforced concrete
US4495238A (en) * 1983-10-14 1985-01-22 Pall Corporation Fire resistant thermal insulating structure and garments produced therefrom
US4508775A (en) * 1983-10-14 1985-04-02 Pall Corporation Gas permeable composite structures
EP0157218A1 (en) * 1984-03-09 1985-10-09 Daikin Industries, Limited Fluorine-containing silane compounds and method of preparing them
US4564552A (en) * 1983-12-28 1986-01-14 Pall Corporation Gas permeable, water and oil resistant composite structure
US4578826A (en) * 1983-12-28 1986-04-01 Pall Corporation Process for the manufacture of protective hand coverings
EP0184479A1 (en) * 1984-11-13 1986-06-11 Elf Atochem S.A. Fluorosilanes and process for their preparation
US4647413A (en) * 1983-12-27 1987-03-03 Minnesota Mining And Manufacturing Company Perfluoropolyether oligomers and polymers
EP0226092A1 (en) * 1985-11-28 1987-06-24 Wakunaga Seiyaku Kabushiki Kaisha Slide glass
EP0227103A2 (en) * 1985-12-23 1987-07-01 AUSIMONT S.p.A. Fluorinated polymers containing fillers and having improved properties
US4742177A (en) * 1986-01-31 1988-05-03 Shin-Etsu Chemical Co., Ltd. Methacrylic acid ester
US4743300A (en) * 1986-08-29 1988-05-10 Minnesota Mining And Manufacturing Company Polyfluoropolyethers having pendant perfluoroalkoxy groups
US4801726A (en) * 1986-04-15 1989-01-31 Northeastern University Repetitive hit-and-run immunoassay and stable support-analyte conjugates; applied to T-2 toxin
US4820588A (en) * 1986-08-29 1989-04-11 Minnesota Mining And Manufacturing Company Shaped articles of polyfluoropolyethers having pendant perfluoroalkoxy groups
US4981727A (en) * 1986-08-29 1991-01-01 Minnesota Mining And Manufacturing Company Polyfluoropolyethers having pendant perfluoroalkoxy groups
EP0452723A1 (en) * 1990-04-03 1991-10-23 Ppg Industries, Inc. Chemically treated glass surface
EP0504796A1 (en) * 1991-03-19 1992-09-23 Hitachi, Ltd. Method for surface treatment of a body, surface treatment agent, surface treated body, surface treated members, and apparatus being furnished with same
EP0508136A2 (en) * 1991-03-14 1992-10-14 Matsushita Electric Industrial Co., Ltd. Surface-treated apparel material
US5288889A (en) * 1992-05-18 1994-02-22 Shin-Etsu Chemical Co. Fluorinated organic silicon compounds and method for making
US5306758A (en) * 1989-12-14 1994-04-26 Minnesota Mining And Manufacturing Company Fluorocarbon-based coating compositions and articles derived therefrom
US5328768A (en) * 1990-04-03 1994-07-12 Ppg Industries, Inc. Durable water repellant glass surface
US5461173A (en) * 1993-12-27 1995-10-24 Shin-Etsu Chemical Co., Ltd. Fluorine-containing organosilicon compound and its manufacture
EP0688762A3 (en) * 1994-06-23 1996-07-03 Shinetsu Chemical Co Organic fluorine compounds and curable compositions containing them
US5578340A (en) * 1991-01-28 1996-11-26 Matsushita Electric Industrial Co., Ltd. Medical member and method of manufacturing the same
US5674967A (en) * 1990-04-03 1997-10-07 Ppg Industries, Inc. Water repellent surface treatment with integrated primer
US5688864A (en) * 1990-04-03 1997-11-18 Ppg Industries, Inc. Autophobic water repellent surface treatment
US5707740A (en) * 1990-04-03 1998-01-13 Ppg Industries, Inc. Water repellent surface treatment with acid activation
US5739369A (en) * 1995-04-20 1998-04-14 Shin-Etsu Chemical Co., Ltd. Water-soluble surface treating agents
US5888290A (en) * 1996-05-24 1999-03-30 Minnesota Mining And Manufacturing Company Composition and process for imparting durable repellency to substrates
US5919886A (en) * 1995-05-29 1999-07-06 Shin-Etsu Chemical Co., Ltd. Room temperature curable fluoropolymer composition; and fluorine-containing organosilicon compounds, a method of producing the same, and room temperature curable silicone composition containing the same
US6025025A (en) * 1990-04-03 2000-02-15 Ppg Industries Ohio, Inc. Water-repellent surface treatment
SG80552A1 (en) * 1995-06-15 2001-05-22 Sumitomo Chemical Co Antireflection filter
US6277485B1 (en) 1998-01-27 2001-08-21 3M Innovative Properties Company Antisoiling coatings for antireflective surfaces and methods of preparation
WO2001064274A2 (en) * 2000-03-01 2001-09-07 Glaxo Group Limited Metered dose inhaler
US6333074B1 (en) * 1996-02-01 2001-12-25 Matsushita Electric Industrial Co., Ltd. Water repellent coating film, method and apparatus for manufacturing the same, and water repellent coating material composition
WO2002030848A1 (en) 2000-10-12 2002-04-18 3M Innovative Properties Company Compositions comprising fluorinated polyether silanes for rendering substrates oil and water repellent
US6461537B1 (en) 1998-01-02 2002-10-08 Ashland Inc. Water repellent glass treatment for automotive applications
US6482911B1 (en) 2001-05-08 2002-11-19 3M Innovative Properties Company Fluoroalkyl polymers containing a cationogenic segment
US20030068486A1 (en) * 2001-09-11 2003-04-10 Arney David S. Smudge resistant nanocomposite hardcoats and methods for making same
DE10149933A1 (en) * 2001-10-10 2003-04-30 Schott Glas Glass and-or ceramic vessel with improved pouring properties, e.g. a coffee pot or milk jug, has a hydrophobic layer on the pouring rim obtained by treatment with poly-alkyl-hydrogen-silane or perfluoroalkylsilane
US6592659B1 (en) 2001-11-15 2003-07-15 3M Innovative Properties Company Compositions for aqueous delivery of fluorinated silanes
US20030161962A1 (en) * 2000-06-06 2003-08-28 Robert Lines Antifouling coating composition comprising a fluorinated resin
US20030207130A1 (en) * 2001-11-27 2003-11-06 3M Innovative Properties Company Compositions for aqueous delivery of self-emulsifying fluorinated alkoxysilanes
US6656258B2 (en) 2001-03-20 2003-12-02 3M Innovative Properties Company Compositions comprising fluorinated silanes and compressed fluid CO2
US20050048288A1 (en) * 2003-08-21 2005-03-03 3M Innovative Properties Company Perfluoropolyether amide-linked phosphonates, phosphates, and derivatives thereof
US20050054804A1 (en) * 2003-09-08 2005-03-10 Dams Rudolf J. Fluorinated polyether isocyanate derived silane compositions
JP2005508420A (en) * 2001-11-08 2005-03-31 スリーエム イノベイティブ プロパティズ カンパニー Coating compositions containing fluorochemical polyether silane polycondensates and their use
JP2005508433A (en) * 2001-11-08 2005-03-31 スリーエム イノベイティブ プロパティズ カンパニー Coating compositions comprising partial condensates of fluorochemical polyether silanes and their use
US20050096244A1 (en) * 2003-10-30 2005-05-05 Audenaert Frans A. Mixture of fluorinated polyethers and use thereof as surfactant
US20050121644A1 (en) * 2003-12-05 2005-06-09 3M Innovative Properties Company Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes
US20060264650A1 (en) * 2005-05-23 2006-11-23 Innovation Chemical Technologies, Ltd. Fluorinated organic silicon coating material
US7294731B1 (en) 2006-08-28 2007-11-13 3M Innovative Properties Company Perfluoropolyether silanes and use thereof
US20080050600A1 (en) * 2006-08-28 2008-02-28 3M Innovative Properties Company Antireflective article
WO2008073689A1 (en) * 2006-12-15 2008-06-19 3M Innovative Properties Company Fluorochemical urethane compounds having pendent silyl groups used for surface treatment
US20100018706A1 (en) * 2006-12-07 2010-01-28 Fan Wayne W Particles comprising a fluorinated siloxane and methods of making and using the same
US20100316868A1 (en) * 2006-10-20 2010-12-16 David Moses M Method for easy-to-clean substrates and articles therefrom
US20110081496A1 (en) * 2009-10-06 2011-04-07 3M Innovative Properties Company Perfluoropolyether Coating Composition for Hard Surfaces
WO2012064653A1 (en) 2010-11-10 2012-05-18 3M Innovative Properties Company Surface treatment process, composition for use therein, and treated article
WO2012064649A1 (en) 2010-11-10 2012-05-18 3M Innovative Properties Company Optical device surface treatment process and smudge-resistant article produced thereby
WO2012064646A1 (en) 2010-11-10 2012-05-18 3M Innovative Properties Company Hydrophobic fluorinated coatings
WO2012173803A1 (en) 2011-06-15 2012-12-20 3M Innovative Properties Company Hydrophobic hydrocarbon coatings
US8410202B1 (en) * 2011-10-24 2013-04-02 Xerox Corporation Coating compositions
CN104245865A (en) * 2012-02-20 2014-12-24 3M创新有限公司 Oleophobic coatings
US9279073B2 (en) 2008-10-07 2016-03-08 Ross Technology Corporation Methods of making highly durable superhydrophobic, oleophobic and anti-icing coatings
WO2016094082A1 (en) 2014-12-08 2016-06-16 3M Innovative Properties Company Fluorinated silane compounds, compositions, and articles
WO2016101185A1 (en) * 2014-12-24 2016-06-30 E. I. Du Pont De Nemours And Company Perfluoropolyether silanes and method of forming the same
US9388325B2 (en) 2012-06-25 2016-07-12 Ross Technology Corporation Elastomeric coatings having hydrophobic and/or oleophobic properties
US9528022B2 (en) 2011-12-15 2016-12-27 Ross Technology Corporation Composition and coating for hydrophobic performance
US9546299B2 (en) 2011-02-21 2017-01-17 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
US10487180B2 (en) 2014-12-08 2019-11-26 3M Innovative Properties Company Compounds comprising modified diorganosiloxane polymers
US20210047540A1 (en) * 2015-09-01 2021-02-18 AGC Inc. Fluorinated ether compound, fluorinated ether composition, coating liquid and article
US11525031B2 (en) * 2017-08-22 2022-12-13 AGC Inc. Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3646085A (en) * 1970-09-24 1972-02-29 Du Pont Perfluoroalkyletheramidoalkyltrialkoxysilanes
US3810874A (en) * 1969-03-10 1974-05-14 Minnesota Mining & Mfg Polymers prepared from poly(perfluoro-alkylene oxide) compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3810874A (en) * 1969-03-10 1974-05-14 Minnesota Mining & Mfg Polymers prepared from poly(perfluoro-alkylene oxide) compounds
US3646085A (en) * 1970-09-24 1972-02-29 Du Pont Perfluoroalkyletheramidoalkyltrialkoxysilanes

Cited By (111)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302571A (en) * 1979-03-16 1981-11-24 Shin-Etsu Chemical Co., Ltd. Room temperature-curable polyoxyalkylene polyether compositions
US4322542A (en) * 1980-01-17 1982-03-30 Varian Associates, Inc. Strong anion exchange composition
US4316041A (en) * 1980-02-19 1982-02-16 Union Carbide Corporation Liquid crystal silanes
US4342796A (en) * 1980-09-10 1982-08-03 Advanced Chemical Technologies, Inc. Method for inhibiting corrosion of internal structural members of reinforced concrete
US4495238A (en) * 1983-10-14 1985-01-22 Pall Corporation Fire resistant thermal insulating structure and garments produced therefrom
US4508775A (en) * 1983-10-14 1985-04-02 Pall Corporation Gas permeable composite structures
US4647413A (en) * 1983-12-27 1987-03-03 Minnesota Mining And Manufacturing Company Perfluoropolyether oligomers and polymers
US4578826A (en) * 1983-12-28 1986-04-01 Pall Corporation Process for the manufacture of protective hand coverings
US4564552A (en) * 1983-12-28 1986-01-14 Pall Corporation Gas permeable, water and oil resistant composite structure
EP0157218A1 (en) * 1984-03-09 1985-10-09 Daikin Industries, Limited Fluorine-containing silane compounds and method of preparing them
EP0184479A1 (en) * 1984-11-13 1986-06-11 Elf Atochem S.A. Fluorosilanes and process for their preparation
EP0226092A1 (en) * 1985-11-28 1987-06-24 Wakunaga Seiyaku Kabushiki Kaisha Slide glass
EP0227103A3 (en) * 1985-12-23 1989-01-25 Ausimont S.P.A. Fluorinated polymers containing fillers and having improved properties
EP0227103A2 (en) * 1985-12-23 1987-07-01 AUSIMONT S.p.A. Fluorinated polymers containing fillers and having improved properties
JPS62246952A (en) * 1985-12-23 1987-10-28 アウシモント・ソチエタ・ペル・アツイオニ Fluorinated polymer containing filler and having improved property
JPH0764973B2 (en) 1985-12-23 1995-07-12 アウシモント・ソチエタ・ペル・アツイオニ Fluorinated polymers containing fillers and having improved properties
US4742177A (en) * 1986-01-31 1988-05-03 Shin-Etsu Chemical Co., Ltd. Methacrylic acid ester
US4801726A (en) * 1986-04-15 1989-01-31 Northeastern University Repetitive hit-and-run immunoassay and stable support-analyte conjugates; applied to T-2 toxin
US4820588A (en) * 1986-08-29 1989-04-11 Minnesota Mining And Manufacturing Company Shaped articles of polyfluoropolyethers having pendant perfluoroalkoxy groups
US4981727A (en) * 1986-08-29 1991-01-01 Minnesota Mining And Manufacturing Company Polyfluoropolyethers having pendant perfluoroalkoxy groups
US4743300A (en) * 1986-08-29 1988-05-10 Minnesota Mining And Manufacturing Company Polyfluoropolyethers having pendant perfluoroalkoxy groups
US5306758A (en) * 1989-12-14 1994-04-26 Minnesota Mining And Manufacturing Company Fluorocarbon-based coating compositions and articles derived therefrom
EP0452723A1 (en) * 1990-04-03 1991-10-23 Ppg Industries, Inc. Chemically treated glass surface
US5328768A (en) * 1990-04-03 1994-07-12 Ppg Industries, Inc. Durable water repellant glass surface
US5707740A (en) * 1990-04-03 1998-01-13 Ppg Industries, Inc. Water repellent surface treatment with acid activation
US6025025A (en) * 1990-04-03 2000-02-15 Ppg Industries Ohio, Inc. Water-repellent surface treatment
US5980990A (en) * 1990-04-03 1999-11-09 Ppg Industries Ohio, Inc. Water repellent surface treatment with acid activation
US5674967A (en) * 1990-04-03 1997-10-07 Ppg Industries, Inc. Water repellent surface treatment with integrated primer
US5688864A (en) * 1990-04-03 1997-11-18 Ppg Industries, Inc. Autophobic water repellent surface treatment
US5578340A (en) * 1991-01-28 1996-11-26 Matsushita Electric Industrial Co., Ltd. Medical member and method of manufacturing the same
EP0508136A3 (en) * 1991-03-14 1993-01-07 Matsushita Electric Industrial Co., Ltd. Surface-treated apparel material
EP0508136A2 (en) * 1991-03-14 1992-10-14 Matsushita Electric Industrial Co., Ltd. Surface-treated apparel material
US5474839A (en) * 1991-03-14 1995-12-12 Matsushita Electric Industrial Co., Ltd. Surface-treated apparel material
EP0504796A1 (en) * 1991-03-19 1992-09-23 Hitachi, Ltd. Method for surface treatment of a body, surface treatment agent, surface treated body, surface treated members, and apparatus being furnished with same
US5346633A (en) * 1991-03-19 1994-09-13 Hitachi, Ltd. Method for surface treatment of a body, surface treatment agent, surface treated body, surface treated members, and apparatus being furnished with same
US5288889A (en) * 1992-05-18 1994-02-22 Shin-Etsu Chemical Co. Fluorinated organic silicon compounds and method for making
US5461173A (en) * 1993-12-27 1995-10-24 Shin-Etsu Chemical Co., Ltd. Fluorine-containing organosilicon compound and its manufacture
EP0688762A3 (en) * 1994-06-23 1996-07-03 Shinetsu Chemical Co Organic fluorine compounds and curable compositions containing them
US5739369A (en) * 1995-04-20 1998-04-14 Shin-Etsu Chemical Co., Ltd. Water-soluble surface treating agents
US5919886A (en) * 1995-05-29 1999-07-06 Shin-Etsu Chemical Co., Ltd. Room temperature curable fluoropolymer composition; and fluorine-containing organosilicon compounds, a method of producing the same, and room temperature curable silicone composition containing the same
US6020450A (en) * 1995-05-29 2000-02-01 Shin-Etsu Chemical Co., Ltd. Room temperature curable fluoropolymer composition; and fluorine-containing organosilicon compounds, a method of producing the same, and room temperature curable silicone composition containing the same
SG80552A1 (en) * 1995-06-15 2001-05-22 Sumitomo Chemical Co Antireflection filter
US6333074B1 (en) * 1996-02-01 2001-12-25 Matsushita Electric Industrial Co., Ltd. Water repellent coating film, method and apparatus for manufacturing the same, and water repellent coating material composition
US5888290A (en) * 1996-05-24 1999-03-30 Minnesota Mining And Manufacturing Company Composition and process for imparting durable repellency to substrates
US6461537B1 (en) 1998-01-02 2002-10-08 Ashland Inc. Water repellent glass treatment for automotive applications
US6277485B1 (en) 1998-01-27 2001-08-21 3M Innovative Properties Company Antisoiling coatings for antireflective surfaces and methods of preparation
WO2001064274A2 (en) * 2000-03-01 2001-09-07 Glaxo Group Limited Metered dose inhaler
WO2001064274A3 (en) * 2000-03-01 2002-02-07 Glaxo Group Ltd Metered dose inhaler
US20030145850A1 (en) * 2000-03-01 2003-08-07 Hailey Mark Andrew Metered dose inhaler
US20030161962A1 (en) * 2000-06-06 2003-08-28 Robert Lines Antifouling coating composition comprising a fluorinated resin
US6899955B2 (en) * 2000-06-06 2005-05-31 International Coatings Limited Antifouling coating composition comprising a fluorinated resin
US6613860B1 (en) 2000-10-12 2003-09-02 3M Innovative Properties Company Compositions comprising fluorinated polyether silanes for rendering substrates oil and water repellent
WO2002030848A1 (en) 2000-10-12 2002-04-18 3M Innovative Properties Company Compositions comprising fluorinated polyether silanes for rendering substrates oil and water repellent
US6656258B2 (en) 2001-03-20 2003-12-02 3M Innovative Properties Company Compositions comprising fluorinated silanes and compressed fluid CO2
US6482911B1 (en) 2001-05-08 2002-11-19 3M Innovative Properties Company Fluoroalkyl polymers containing a cationogenic segment
US7101616B2 (en) 2001-09-11 2006-09-05 3M Innovative Properties Company Smudge resistant nanocomposite hardcoats and methods for making same
US20030068486A1 (en) * 2001-09-11 2003-04-10 Arney David S. Smudge resistant nanocomposite hardcoats and methods for making same
DE10149933A1 (en) * 2001-10-10 2003-04-30 Schott Glas Glass and-or ceramic vessel with improved pouring properties, e.g. a coffee pot or milk jug, has a hydrophobic layer on the pouring rim obtained by treatment with poly-alkyl-hydrogen-silane or perfluoroalkylsilane
JP2005508420A (en) * 2001-11-08 2005-03-31 スリーエム イノベイティブ プロパティズ カンパニー Coating compositions containing fluorochemical polyether silane polycondensates and their use
JP2005508433A (en) * 2001-11-08 2005-03-31 スリーエム イノベイティブ プロパティズ カンパニー Coating compositions comprising partial condensates of fluorochemical polyether silanes and their use
US6592659B1 (en) 2001-11-15 2003-07-15 3M Innovative Properties Company Compositions for aqueous delivery of fluorinated silanes
US20030207130A1 (en) * 2001-11-27 2003-11-06 3M Innovative Properties Company Compositions for aqueous delivery of self-emulsifying fluorinated alkoxysilanes
US6861149B2 (en) 2001-11-27 2005-03-01 3M Innovative Properties Company Compositions for aqueous delivery of self-emulsifying fluorinated alkoxysilanes
US7678426B2 (en) 2003-08-21 2010-03-16 3M Innovative Properties Company Perfluoropolyether amide-linked phosphonates, phosphates, and derivatives thereof
US20050048288A1 (en) * 2003-08-21 2005-03-03 3M Innovative Properties Company Perfluoropolyether amide-linked phosphonates, phosphates, and derivatives thereof
WO2005026236A1 (en) 2003-09-08 2005-03-24 3M Innovative Properties Company Fluorinated polyether isocyanate derived silane compositions
US20050054804A1 (en) * 2003-09-08 2005-03-10 Dams Rudolf J. Fluorinated polyether isocyanate derived silane compositions
US7652115B2 (en) 2003-09-08 2010-01-26 3M Innovative Properties Company Fluorinated polyether isocyanate derived silane compositions
US7141537B2 (en) 2003-10-30 2006-11-28 3M Innovative Properties Company Mixture of fluorinated polyethers and use thereof as surfactant
US20050096244A1 (en) * 2003-10-30 2005-05-05 Audenaert Frans A. Mixture of fluorinated polyethers and use thereof as surfactant
US7803894B2 (en) 2003-12-05 2010-09-28 3M Innovatie Properties Company Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes
US20050121644A1 (en) * 2003-12-05 2005-06-09 3M Innovative Properties Company Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes
US7674927B2 (en) 2005-05-23 2010-03-09 Innovation Chemical Technologies, Ltd Fluorinated organic silicon coating material
US20060264650A1 (en) * 2005-05-23 2006-11-23 Innovation Chemical Technologies, Ltd. Fluorinated organic silicon coating material
US7294731B1 (en) 2006-08-28 2007-11-13 3M Innovative Properties Company Perfluoropolyether silanes and use thereof
WO2008027698A1 (en) * 2006-08-28 2008-03-06 3M Innovative Properties Company Antireflective article
US20080050600A1 (en) * 2006-08-28 2008-02-28 3M Innovative Properties Company Antireflective article
JP2010502784A (en) * 2006-08-28 2010-01-28 スリーエム イノベイティブ プロパティズ カンパニー Perfluoropolyether silane and use thereof
US7553514B2 (en) 2006-08-28 2009-06-30 3M Innovative Properties Company Antireflective article
CN101501046B (en) * 2006-08-28 2015-06-03 3M创新有限公司 Perfluoropolyether silanes and use thereof
US20100316868A1 (en) * 2006-10-20 2010-12-16 David Moses M Method for easy-to-clean substrates and articles therefrom
US8158264B2 (en) 2006-10-20 2012-04-17 3M Innovative Properties Company Method for easy-to-clean substrates and articles therefrom
US8236737B2 (en) 2006-12-07 2012-08-07 3M Innovative Properties Company Particles comprising a fluorinated siloxane and methods of making and using the same
US20100018706A1 (en) * 2006-12-07 2010-01-28 Fan Wayne W Particles comprising a fluorinated siloxane and methods of making and using the same
US20100089290A1 (en) * 2006-12-15 2010-04-15 Clark Gregory D Fluorochemical urethane compounds having pendent silyl groups used for surface treatment
US8002886B2 (en) 2006-12-15 2011-08-23 3M Innovative Properties Company Fluorochemical urethane compounds having pendent silyl groups used for surface treatment
WO2008073689A1 (en) * 2006-12-15 2008-06-19 3M Innovative Properties Company Fluorochemical urethane compounds having pendent silyl groups used for surface treatment
CN101541816B (en) * 2006-12-15 2014-03-12 3M创新有限公司 Fluorochemical urethane compounds having pendent silyl groups used for surface treatment
US9926478B2 (en) 2008-10-07 2018-03-27 Ross Technology Corporation Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US9279073B2 (en) 2008-10-07 2016-03-08 Ross Technology Corporation Methods of making highly durable superhydrophobic, oleophobic and anti-icing coatings
US8268067B2 (en) 2009-10-06 2012-09-18 3M Innovative Properties Company Perfluoropolyether coating composition for hard surfaces
US20110081496A1 (en) * 2009-10-06 2011-04-07 3M Innovative Properties Company Perfluoropolyether Coating Composition for Hard Surfaces
WO2011043973A1 (en) 2009-10-06 2011-04-14 3M Innovative Properties Company Perfluoropolyether coating composition for hard surfaces
US9914849B2 (en) 2010-03-15 2018-03-13 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
WO2012064649A1 (en) 2010-11-10 2012-05-18 3M Innovative Properties Company Optical device surface treatment process and smudge-resistant article produced thereby
WO2012064653A1 (en) 2010-11-10 2012-05-18 3M Innovative Properties Company Surface treatment process, composition for use therein, and treated article
WO2012064646A1 (en) 2010-11-10 2012-05-18 3M Innovative Properties Company Hydrophobic fluorinated coatings
US10240049B2 (en) 2011-02-21 2019-03-26 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
US9546299B2 (en) 2011-02-21 2017-01-17 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
WO2012173803A1 (en) 2011-06-15 2012-12-20 3M Innovative Properties Company Hydrophobic hydrocarbon coatings
US8410202B1 (en) * 2011-10-24 2013-04-02 Xerox Corporation Coating compositions
US9528022B2 (en) 2011-12-15 2016-12-27 Ross Technology Corporation Composition and coating for hydrophobic performance
CN104245865A (en) * 2012-02-20 2014-12-24 3M创新有限公司 Oleophobic coatings
US9296918B2 (en) 2012-02-20 2016-03-29 3M Innovative Properties Company Oleophobic coatings
US9388325B2 (en) 2012-06-25 2016-07-12 Ross Technology Corporation Elastomeric coatings having hydrophobic and/or oleophobic properties
US10233285B2 (en) 2014-12-08 2019-03-19 3M Innovative Properties Company Fluorinated silane compounds, compositions, and articles
WO2016094082A1 (en) 2014-12-08 2016-06-16 3M Innovative Properties Company Fluorinated silane compounds, compositions, and articles
US10487180B2 (en) 2014-12-08 2019-11-26 3M Innovative Properties Company Compounds comprising modified diorganosiloxane polymers
WO2016101185A1 (en) * 2014-12-24 2016-06-30 E. I. Du Pont De Nemours And Company Perfluoropolyether silanes and method of forming the same
US20210047540A1 (en) * 2015-09-01 2021-02-18 AGC Inc. Fluorinated ether compound, fluorinated ether composition, coating liquid and article
US11525031B2 (en) * 2017-08-22 2022-12-13 AGC Inc. Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method

Similar Documents

Publication Publication Date Title
US3950588A (en) Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes)
US6395331B1 (en) Transparent substrate bearing an anti-stain, hydrophobic coating, and process for making it
JP4988598B2 (en) A composition containing C4-Kashio silane
US5605958A (en) Composition for surface treatment
US6506496B1 (en) Composition for providing a non-wettable coating, articles coated therewith, and methods for preparing the same
JP2877616B2 (en) Hydrophilic oil repellent treatment agent
US6776834B2 (en) Composition for treating substrate and process of treatment
WO2002030848A1 (en) Compositions comprising fluorinated polyether silanes for rendering substrates oil and water repellent
US20090087646A1 (en) Coated substrate, composition for treating a substrate and process of treatment
US5080824A (en) Cleaner and/or conditioners containing organopolysiloxanes for glass-ceramic surfaces
KR20190115660A (en) Coating composition of glass for bathroom and method for coating using thereof
JPS58172244A (en) Surface treating agent for glass
JPS58172246A (en) Surface treating agent for glass
US3620820A (en) Antiwetting methods and compositions
JP3649585B2 (en) Water repellent coating solution
JP4522357B2 (en) Manufacturing method for water slidable glass articles
JPH0759699B2 (en) Water and oil repellent composition
JPH09157636A (en) Surface treating agent and its production
AU737281B2 (en) Transparent substrate bearing an anti-stain, hydrophobic coating, and process for making it
KR0148069B1 (en) Water repellent for a glass
EP0471324A2 (en) Water-repellant composition
JP2000129247A (en) Surface treatment agent, surface treating agent composition, surface treatment method, and substrate treated therewith
JP3628881B2 (en) Manufacturing method of water repellent liquid and water repellent substrate
WO2010134545A1 (en) Waterdrop slidable article and method for producing same
JP2005255720A (en) Surface composition of glass having stainproof property imparted by water repellency/oil repellency and high washing property imparted by hydrophilic property and treating method